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Hydroalkylation of alkenes with 1,3-diketones via gold(III) or silver(I) catalysis: divergent mechanistic pathways revealed by a DFT-based investigation
journal contribution
posted on 2023-05-20, 23:14 authored by Jalali, M, Hyland, CJT, Alexander BissemberAlexander Bissember, Brian YatesBrian Yates, Alireza AriafardAlireza AriafardDensity functional theory calculations were used to investigate the mechanisms of established hydroalkylation reactions of styrenes with 1,3-diketones that are promoted by either AuCl3/AgOTf or AgOTf catalyst systems. In the former case, our studies led us to propose an original mechanism that is initiated by the generation of highly electrophilic Au(OTf)3, which then coordinates the enol tautomer of the 1,3-diketone substrate. The ensuing highly Brønsted acidic π-complex serves to protonate the styrene to generate a relatively low-energy benzylic carbocation. Notably, this suggests that this benzylic carbocation represents the true catalytic species in the reaction, and thus, the role of the gold complex is solely to generate this active catalyst. AuCl3 alone does not serve as a good initiator for this process because it is not electrophilic enough to generate the relatively low-energy benzylic carbocation. Our investigation of the hydroalkylation facilitated by the slightly electron-deficient AgOTf catalyst revealed that an alternative mechanism predominates. Specifically, it is more likely that the reaction proceeds via a demetallation process directly mediated by the silver catalyst. We found a clear trend indicating that the electron deficiency of the metal center dictates which of these two mechanistic scenarios occurs. This article discusses these two mechanistic pathways in detail, providing key information for the experimental development of hydroalkylation processes.
Funding
Australian Research Council
University of Wollongong
History
Publication title
ACS CatalysisVolume
11Issue
9Pagination
5795-5807ISSN
2155-5435Department/School
School of Natural SciencesPublisher
American Chemical SocietyPlace of publication
United StatesRights statement
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